Uranium separation process



March 13, 1956 A THUNAES ET Al. 2,738,253

URANIUM SEPARATION PROCESS origial Filed May 1, 1951 ACID (/z H2 so4 /5 .a/HR.)

Ac/o WASH REM/PER l l Y l ARVID THUNAES ERNEST ARTHUR BROWN Fig. j. HARoLn wrLuAM SMITH JUHN BRANNE N /NVENTORS A TTORNE Y.;

2,738,253 URANnIM SEPARATION PROCESS Arvid Thunaes, Ernest Arthur Brown, and Harold William Smith, Ottawa, ntario, and .lohn Brannen, Brittania Bay, Ottawa, Ontario, Canada, assignors to Eldorado Mining and Reining Limited, Ottawa, (bntario, Canada, a corporation ot Canada Continuation of application Serial No. 224,063, May 1, 1951. This application August 10, 1953, Serial No. 373,387

Claims priority, application Canada November 22, 1949 6 Claims. (Cl. 23-14.5)

This process relates to the separation of uranium from its ores and more particularly to an acid leaching process for dissolving uranium from its ores.

This is a continuation of application 224,063, tiled May l, 1951, now abandoned.

Previously, acid leaching of pitchblende and other uranium bearing ores has been confined largely to treatment oi' high-grade products such as gravity concentrates or picked ore. In these processes hot concentrated acid solutions play an important part and roasting of the feed is often a preliminary step. Nitric acid or a nitrate is usually used as an oxidizing agent. The use of concentrated acid solutions and the relatively high concentration of oxidizing agent if nitric acid or a nitrate is employed would be uneconomical in the treatment of low-grade and complex ores. The use of ferric sulphate as an oxidizing agent had previously been considered but the use of this reagent has certain disadvantages, as will appear subsequently.

The object of the present process is to provide a method for the economical extraction of uranium which may be used not only for the treatment of high-grade products but for low-grade ores and complex ores which contain, for example, cobalt, nickel, copper, iron, manganese, bismuth, lead, arsenic, sulphur, phosphorous and carbonate minerals.

In general the present process comprises conversion of such of the uranium as is present in the tetravalent state to the hexavalent state by means of a strong oxidizing agent and the dissolution of uranium in the hexavalent state by weak solutions of sulphonic acid. This process is carried out at a low pH and maintaining an oxidizing condition to keep uranium in solution in the presence of arsenate and phosphate. Copending application Serial No. 224,062, tiled May 1, 1951, describes a methodfor the recovery of uranium from the dilute suphuric acid leach solutions thus produced.

Figure l illustrates diagrammatically the basic leaching flowsheet.

The ore is first suitably ground, the degrees of neness depending upon the grain size at which substantially all the uranium minerals are liberated, that is, made accessible to attack by the leach solutions. The majority of pitchblende ores should be ground to minus 40 mesh.

With some types of ore additional treatment of the leach feed will be advantageous such as, for example, the removal of certain constituents of the ore by froth otation. Arsenides and sulphides may be separated as a flotation concentrate for subsequent separate leaching since a considerable proportion of the uranium may be intimately associated with sulphides and arsenides which generally require a greater concentration of oxidizing agent. Carbonate minerals may be partly removed by dotation in order to reduce acid consumption. The amount of such carbonate minerals which should be re- -moved will depend upon economic factors and on the vloss of UaOs in the carbonate froth product.

2,738,253 Patented Mar. 13, 1956 The ore pulp is fed into an agitator designated on the flowsheet as No. 1 agitator. Sodium chlorate, sulphuric acid and, if required, water are added in this agitator. Sodium chlorate has been found to be the most suitable oxidizing agent for this process although other strong oxidizing agents may be used. An oxidizing agent is used because cold dilute sulphuric acid alone will not dissolve U02 at a useful rate but will do so quite readily if an oxidizing agent is present. An additional reason for using an oxidizing agent is that the uranium which has been dissolved in the leach solution should be kept in the hexavalent (uranyl) form. If the uranium is allowed to become reduced to the tetravalent (uranous) form by reducing agents introduced with or leached from the ore, it may bey precipitated by impurities in the solution such as phosphate or arsenate, even at pH Values well below 2. Hexavalent uranium also is precipitated by these ions but at higher pH values, thus the uranium may be kept in solution by control of the pH.

Sodiurn chlorate is particularly suitable as an oxidizing agent since it will maintain in substantially a completely oxidized condition, elements such as uranium and iron. All known uranium ores contain some iron mineral soluble in weak sulphuric acid. Sodium chlorate, being one of the most powerful oxidizing agents known, will oxidize substantially all ferrous irons to ferric and the elimination of ferrous iron will drive the following reaction to the right.

Tetravalent uranium-i-ferric iron;`

Hexavalent uranium-i-ferrous iron The reaction of the chlorate ion itself, to oxidize other ions and form chloride ions, is not reversible Yin leach solutions. In addition, ores ground by steel equipment will generally contain significant amounts of metallic iron. In the presence of an active reducing agent such as this, hexavalent uranium will be reduced to tetravalent uranium which can be precipitated by arsenates or phosphates even at pH values as low as 1.3. If a less effective oxidizing agent such as ferric sulphate be used this metallic iron will be oxidized only as far as the ferrous condition and the considerations previously set forth will apply. Sodium chlorate, on the other hand, is suiiiciently powerful as an oxidizing agent to take the metallic iron to the ferric form.

Another advantage in using sodium chlorate is the small weight of reagent required. it may be calculated from the following equations that l part of sodium chlorate by weight as oxidizing agent is equivalent to 2.45 parts by weight of MnO2 or 11.26 parts by weight of Fe2(SO4)a in oxidizing the sarne amount of uranium from the tetravalent to the hexavalent form.

it will also be clear from examination of these equations that the oxidation reaction with sodium chlorate requires only one half of the acid consumed in the oxidation reaction using manganese dioxide. The oxidation reaction in which ferrie sulphate is used as oxidizing agent consumes no acid, but the amount of ferrie sulphate required more than offsets the acid consumed by the sodium chlorate reaction. if manganese dioxide or ferrie sulphate is used in place of sodium chlorate as oxidizing agent the quantity of oxidizing agent required may be further increased since ferric and manganic ions will precipitate with phosphate and arsenate ions at pH values as low as 1.2. The oxidizing ion C103 provided by sodium chlorate is not precipitated by phosphate and arsenate at low pH values. In view of the weight advan-tage. it is cheaperv to` use sodium chlorate than either ferricsulphateor manganeseA dioxide atthe reagent prices and transportation costs prevailing at the date of this application and as has been seen sodium chlorate is more effective. l

The amount of sodium chlorate which should be added to, No. 1 agitator varies withl the particular ore being treated but a typical quantity is shown inthe flowsheet illustrated in Figure l in which the ratio between ore and sodium chlorate is 40 lb./hr. dry weight to 0.07 lb./hr. The amount of sodium chlorate added should be sufiicient to leave a slight excess at the endv of agitation and maintain, substantially all dissolved iron. in the ferrie state. The sulphurick acid is also added to agitator No. l in quantities sufcient to maintain the pH atl below 2 and preferably between 1.6 and 1.8. The sulphuric acid dissolves hexavalent uranium and acts with the oxidizing agent to dissolve tetravalent uranium. Low pH- values are maintained at this stage and throughout the process to prevent the precipitation of uranium by impurities in the solution, particularly phosphates and arsenates.

Instead of sodium chlorate, other strong oxidizing agents such as potassium chlorate, chloric acid or sodium persulphate may be used.

The tolerance of uranyl sulphate solution for arsenate is shown by. Experimenty 1 which illustrates andjustifies the importance of conducting the process atv a low pH.

EXPERIMENT 1 To samples of uranyl sulphate solution containing the equivalent of 1.25 grams U30@ per litre was added sulphuric acid to bring the pH to the initial values shown below. Sodium arsenate solution containing 18.9 grams of arsenic per litre was added until a noticeable precipitate formed and the pH at which this occurred was noted. The amount or" arsenic added is expressed in equivalents, an equivalent being the amount required to form UO2HASO4 with the uranium in the sample.

pH of uranium Solutlon Arsenic added tg precipitta- At precip- 10T? P0111 Initial itation equivalents point ln Experiment 2 the importance of low pH in the presence phosphates is illustrated by showing the tolerance of uranyl sulphate solution for phosphate.

EXPERIMENT 2 To samples of uranyl sulphate solution of pH 0.9, l litre==l gram UaOa, was added phosphoric acid solution of pH 1.7, l litre=2.53 grams P205. Sodium hydroxide was added where necessary to adjust the pH to the values given below. The amount of P205 added is expressed in equivalents. an equivalent being the amount stoichiometrically required for formation of UO2HPO4 with the uranium in the sample.

It will' be4 evident, from, the foregoing that the addition 4 of acid must be regulated to maintain a pH value in the pulp, of 1.5-2,0. and. preferably 1.6 to 1.8 where thevore contains arsenic or phosphorous. The pH may be higher if these elements are absent. The lower pH limit inserted above of 1.5 is not as critical as the upper limit but rather marks the point at which it is no longer necessary or economical further to reduce the pH by increasing the concentration of sulphuric acid; It will also be clear, from the experimental results given above, that slight variations in the upper pH limit will occur in different ores; thus it the ore contains only small quantities of arsenates and phosphates an upper limit of 2.0 may be used, if the ore. contains a greater proportion. of these impurities the pH must not be allowed to rise above 1.8. l

The sulphuric acid is added cold and diluted to agitator No. l in sufficient quantities to maintainl the desired pH. Any convenient strength of sulphuric acid can be used providing the concentration is suitable for pH control at the operating pulp density. Water may alsobe added to agitator No. l to; adjust the liquidzsolids ratio. Adjustment of the total to 506Q% solids has giveny good re,-

sults.

The pulp density may be varied but a ratiov of about 3 liquid to 4 solids may be readily handled by subsequent filtering without preliminary thickening: also the resulting leach solution contains a greater concentration of uranium when.Y a minimum; of liquid is used per unit of solids. The, orepulpmay, if necessary, be filtered before being fed into No. l agitator to increase the pulp density.

A moderate amount of agitation is suicient, such as may be obtained bythe agitators commonly usedA in the cyanidationA process but usingk only a minimum of rake speed, and air. The total time of agitation will depend on the orel and isj determined by the point at which the value of, the uranium extracted per unit time becomes less than the costA of treatment: for` one type o f ore the total agitation time thus selected was 24 hours. 'I 'hat is to say, 24 hours elapsedi from the time ore was added to agitator No.y l tol the time the pulp was discharged from agitator. No. 3.

Temperature of the pulp may be varied but it ispreferable to. use a. low temperature of 10-.15 C. since the dissolution of uranium minerals is not appreciably retarded by low temperatures and the acid consumption by ganguej minerals4r generally decreases withdecreasing pulp temperatures to an extent which offsets such retardation of the dissolution of uranium minerals as occurs.

The ilowsheet shows threeagitators in series. Reagents as describedy above are added continuously to agitator No. 1. Agitator No. 3Ydischarges to No. l filter. Fora continuousprocess a` minimum; of three agitators in'series should be used to yreduce short circuiting.

Additional: acid. is added to agitators Nos. 2- and 3 to maintain the pHl betweenk 1.8-2.1. Where the pH is allowed to riseV as high as 2.1 in agitators Nos. 2 and 3, therev will. be appreciablel reprecipitation of hexavalent uranium as arsenate and phosphate if the ore contains these. impurities. A repulping step will therefore be necessary tov dissolve this precipitate if a relatively high pH is used. If it'is desired to omit thev repulping step the pH should. be-V maintained at 1.6-1.8 in agitators Nos. 2 and 3.

The pulp leaving agitator No. 3 is discharged in to a filter. for separation of the uranium bearing liquor. The filter cake-- is washed:y with-,weak acid solution and finally with water. Double filtration isv preferable for ores which contain soluble arsenic and phosphates. Between the iirst and second filter a repulping step is introduced in which the cake from the first filter is repulped with 1 to 2% sulphuric acidwhich may contain a small amount of sodium chlorate. The additionof sodium chloratein the repulping stepjnay be, omittedif a slight excessof sodium chlorate, hasy been aclfgledto agitator No. 1 since there will then. be somersidualodium chlorate in. the leach liquor. Although dissolution. of precipitatesk of hexavalent uranium as arsenate and phosphate will occur in the repulping step, in view of the residual sodium chlorate in the leach liquor the repulpingstep would not have to redissolve any precipitate of tetravalent uranium. The time of contact during repulping may be 5-10 minutes and it Will be observed that a substantial saving of acid is achieved compared with a process in which a suiciently low pH value is maintained during the whole of the agitation period to prevent reprecipitation of the uranium. Repulping is particularly advantageous where the ore contains minerals slightly solube in acid such as, for example, carbonates. Another advantage of repulping is that less reagent is required for a reduction process such as is described in copending application Serial No. 224,062 if the pH is comparatively high.

After repulping, the pulp is passed to the second lter where it is washed with 1% sulphuric acid followed by water. The amount of wash acid is determined by tests with a particular ore, acid consumption and the cost of treating additional solution being balanced against increased uranium recovery. A typical quantity of lb./hr. of acid wash to 40 lb./hr. dry weight of ore is shown in the owsheet.

The residue from No. 2 filter is discharged as waste. The iiltrates and wash solution from No. 1 and No. 2 filters are combined in the case of complex ores and are given further treatment such as is described in copending patent application Serial No. 224,062 to extract uranium from the leach solution. If the ore does not contain significant amounts of detrimental impurities it may, as an alternative to combining the ltrates, be advantageous to recirculate the wash solution from lters 1 and 2 and the leach solution from filter 2 or one or more of these solutions may be recirculated to the rst agitator to build up the uranium content of the solution which passes to the precipitation process and to reduce acid consumption.

Example 1 which follows gives the results of a laboratory test carried out in accordance with the process described in this application.

Example 1 ASSAY 0F ORE TREATED Percent U30a 0.305 CO2 3.36 Fe 3.38 As 0.35 P205 1.15

SIZE ANALYSIS Mesh: Weight percent 100 9.45 -100-l-150 11.65 -150-1-200 14.10 -200-1-325 14.80 -325 mesh 32.40 -325 slimes 17.60

500 grams of ore (dry weight) were leached for 24 hours at a temperature of C. and at a dilution of 4 grams ore to 3 ccs. solution. Sodium chlorate, 5 lbs. per ton ore was added at the beginning of the leach agitation.

For the first seven hours of agitation the pulp was controlled at pH 1.5 by adding sulphuric acid when required. In the remaining 17 hours of the leach time no more sulphuric acid was added and the pH has risen to a final value of 2.1 at the end of the 24 hour agitation period.

The pulp was then tiltered and the llter cake was given a replacement wash with 125 cc. of 1% sulphuric acid (i. e. 500 lbs. 1% acid solution per ton ore).

'Ihe filter cake was then repulped by agitation with 185 cc. of Water (740 lbs. Water per t0n ore) to which sulphuric acid Was added to bring the pH of the pulp to 1.20 (4 lbs. 100% H2804 per ton ore). The contact time in repulping was approximately 4 minutes. The pulp was filtered and the filter cake washed once with 125 cc. of 1% sulphuric acid (500 lbs. 1% acid per ton ore) followed by a final wash with 125 cc. water (500 lbs. per ton ore). The first acid wash filtrate (the wash preceding the repulping step) was combined with the original leach liquor, since it was a replacement Wash and the solution it displaced fromv the filter cake would be that portion of the leach liquor retained as moisture by the cake formed in ltering the original leach pulp.

The ltrates, from the repulping and subsequent washing steps were combined but kept separate from the liltrates above for the purposes of this test to enable the proportion of uranium recovered by the repulping step to be ascertained. No oxidizing agent was added in the repulping step.

The test was conducted at 20 C. Table 1 shows that the extraction of uranium was 88.7%, nearly a third of which was recovered through the repulping step in view of the high pH of 2.1 at the end of agitation.

Table 1 Wt., V01., Fe, AS, P205, Usos, gms ccs. Grams Grams Grams Grams Ore treated 500 16. 1. 75 5. 75 1.525

Filtrate from leach and first wash 335 0. 767 0. 22S 0.067 0.925 Filtrate from repulping step and final Washes 445 0. 445 0.227 0. 062 0.427

Total in nitrates 1. 212 0. 455 0.129 1. 352

Residue 480 15. 69 1. 30 5. 62 0. 173

Percent of total in cornbined ltrates 7. 2 26.0 2. 2 88. 7

It will be appreciated from the foregoing that the process which has been described constitutes a highly economical and practical method for the treatment not only of high-grade uranium ores but of low-grade and complex ores.

We claim: Y

1. A process for dissolving uranium from ores containing ferrous iron minerals and tetravalent uranium in which uranium is brought into solution by agitating the ore with cold dilute sulphuric acid sufficient to maintain a highly acid reaction condition of a pH of less than 2.1 in the presence of sodium chlorate in an amount sufficient to oxidize substantially all ferrous iron to ferrie and to convert substantially all tetravalent uranium to hexavalent uranium, and to maintain the uranium in a hexavalent condition.

2. A process for dissolving uranium from ores containing ferrous iron minerals, metallic iron and tetravalent uranium in which uranium is brought into solution by agitating the ore with cold dilute sulphuric acid sufficient to maintain a lhighly acid reaction condition of a pH of 1.5 to 2.1 in the presence of sodium chlorate in an amount sufficient to oxidize substantially all ferrous iron to ferrie and substantially all metallic iron to ferrie iron and to convert substantially all tetravalent uranium to hexavalent uranium and to maintain the uranium in a hexavalent condition.

3. A process for dissolving uranium from complex ores containing ferrous iron and elements such as arsenic and phosphorous and in which uranium occurs in the tetravalent form in which uranium is brought into solution by cold dilute sulphuric acid suflicient to maintain a pH of slightly less than 1.8 in the presence of sodium chlorate in an amount suiiicient to oxidize substantially all ferfous iron to ferric and to convert substantially all tetravalent uranium to hexavalent uranium and to maintain the uranium in a hexavalent condition.

4. A process for dissolving uranium from complex ores containing ferrous iron and elements such as arsenic and phosphorous and in which uranium, occurs in the, tetravalenjc form in which uranium is, brought in toj solution by vagitation withV cold dilute sulphllricv acid,l sufficient. for a QH of slightly, less than 1,8 at the commencement of agitation and a pH, of less than, 2.1i at the termination of the agitation period in theprescnqe. of an oxidizing agent containing the chlorate radicall suficient to oXidize substantially al1 ferrous iron to ferrie and to. convert substantially al1 tetravalent uranium to hexavalent uranium and to'maintain the uranium in a hexavalent condition and in which the ore is subsequently ltered'and repulpedwith additional cold dilute sulphuric. acid and then reltered.

5'. A process as described in, claim 4 in which sodium chlorate is used as the oxidizingvagent.

6. A process for dissolvingA uranium from ores conf' t taining ferrous iron and tetravalent uranium ini which uranium is brought into solution as uranyl' sulphate. by agitation with cold dilute sulphuric acidfsuflicient, forv a p H o slightly less than 1,8 at the commencement of agitation anda pH of less than 2.1 at thetermination of the agitation period in. the presence of sodium chlorate in an amount sufci'ent toy oxidi'ze substantially all ferrous iron to ferrie, and to convert substantially all reti-.avalent uranium to hexavalent uranium and to maintain the uranium in a hexavalent condition and in which the ore is subsequently ltered' and repulpednwith additional cold dilute sulphuric. acid' and additional oxidizing agent and then reltered'.

References Cited in the leV of this patent UNITE-D ST ATES. PATENTSS 1,437,191 Paul Nov. 28, 1922 1,471,514 Elliot O'ct. 2.3,l 1923 2,176,610 Starnberg Oct. 17, 1939 2,199,696 Fleck Mayr?,v 1940 OTHER REFERENCES MacTaggart: The Industrial Chemis,t, ,vo1.v 1,8,v pages 421-426V (Nov. 1942). 

1. A PROCESS FOR DISSOLVING URANIUM FROM ORES CONTAINING FERROUS IRON MINERALS AND TETRAVALENT URANIUM IN WHICH URANIUM IS BROUGHT INTO SOLUTION BY AGITATING THE ORE WITH COLD DILUTE SULPHURIC ACID SUFFICIENT TO MAINTAIN A HIGHLY ACID REACTION CONDITION OF A PH OF LESS THAN 2.1 IN THE PRESENCE OF SODIUM CHLORATE IN AN AMOUNT SUFFICIENT TO OXIDIZE SUBSTANTIALLY ALL FERROUS IRON OF FERRIC AND TO CONVERT SUBSTANTIALLY ALL TETRAVALENT URANIUM TO HEXA- 